1. Field of the Invention
This invention relates to a non-aqueous electrolyte secondary battery negative electrode material which exhibits a high charge/discharge capacity and satisfactory cycle performance when used as the negative electrode active material in lithium ion secondary batteries, a method for preparing the same, and a lithium ion secondary battery. Throughout the specification, the term “conductive” or “conductivity” refers to electrically conductive or electric conductivity.
2. Background Art
With the recent remarkable development of potable electronic equipment, communications equipment and the like, a strong demand for high energy density secondary batteries exists from the standpoints of economy and size and weight reductions. One prior art method for increasing the capacity of secondary batteries is to use oxides as the negative electrode material, for example, oxides of V, Si, B, Zr, Sn or the like or complex oxides thereof (see JP-A 5-174818 and JP-A 6-060867 corresponding to U.S. Pat. No. 5,478,671), metal oxides quenched from the melt (JP-A 10-294112), silicon oxide (Japanese Patent No. 2,997,741 corresponding to U.S. Pat. No. 5,395,711), and Si2N2O and Ge2N2O (JP-A 11-102705 corresponding to U.S. Pat. No. 6,066,414). Conventional methods of imparting conductivity to the negative electrode material include mechanical alloying of SiO with graphite, followed by carbonization (see JP-A 2000-243396 corresponding to EP 1032062), coating of silicon particles with a carbon layer by chemical vapor deposition (JP-A 2000-215887 corresponding to U.S. Pat. No. 6,383,686), and coating of silicon oxide particles with a carbon layer by chemical vapor deposition (JP-A 2002-42806).
These prior art methods are successful in increasing the charge/discharge capacity and energy density, but are not necessarily satisfactory because of insufficient cycle performance and failure to fully meet the characteristics required in the market. There is a desire for further improvement in energy density.
In particular, Japanese Patent No. 2,997,741 uses silicon oxide as the negative electrode material in a lithium ion secondary battery to provide an electrode with a high capacity. As long as the present inventors have confirmed, there is left a room for further improvement as demonstrated by a still high irreversible capacity on the first charge/discharge cycle and cycle performance below the practical level. With respect to the technique of imparting conductivity to the negative electrode material, JP-A 2000-243396 suffers from the problem that solid-to-solid fusion fails to form a uniform carbon coating, resulting in insufficient conductivity. In the method of JP-A 2000-215887 which can form a uniform carbon coating, the negative electrode material based on silicon undergoes excessive expansion and contraction upon adsorption and desorption of lithium ions, and is thus impractical. Since the cycle performance lowers, the charge/discharge quantity must be limited in order to prevent the cycle performance from degrading. In JP-A 2002-42806, despite a discernible improvement of cycle performance, due to precipitation of silicon crystallites, insufficient structure of the carbon coating and insufficient fusion of the carbon coating to the substrate, the capacity gradually lowers as charge/discharge cycles are repeated, and suddenly drops after a certain number of charge/discharge cycles. This approach is thus insufficient for use in secondary batteries.